长链支化聚丙烯的非线性流变行为

通过大幅振荡剪切试验方法, 研究了长链支化聚丙烯的非线性流变学行为, 揭示了长链支化结构与非线性黏弹响应的关系. 利用傅里叶变换流变学方法得到试样的三次倍频相对振幅I_3/1与应变的标度关系, 用于界定线性聚丙烯和长链支化聚丙烯非线性流变行为的差异, 并定义了非线性系数来量度长链支化程度. 在高应变下, I_3/1与应变的变化关系可以进一步描述长链支化在非线性流场下的特性, 并得到了长链支化程度与其非线性响应之间的变化关系. 通过应力波的Lissajous曲线分解, 发现了环内和环间黏弹性的差异, 长链支化结构在大应变流场下的非线性黏弹性响应弱于线性结构, 支化程度越高非线性响应越弱.     

茂金属聚乙烯分子链流变学模型研究进展

茂金属聚乙烯的分子链长支化结构对其流变特性有重要影响，长支链可以使熔体弹性和剪切变稀效应明显增强。本文介绍了茂金属聚乙烯分子链模型建立的理论依据，从流变学角度综述了近年来茂金属聚乙烯分子链结构模型的研究进展，阐述了有关的长链支化结构模型及其与流变性能的关系。     

聚合物基粘土纳米复合材料的流变行为研究

聚合物基粘土纳米复合材料具有与常规颗粒填充体系类似的流变特性 :在整个频率范围内 ,储能模量和损耗模量均随粘土含量的增加而变高 ,其频率依赖性会表现出非未端行为 :且当粘土含量超过临界值以后 ,储能模量会在低频区表现出似固体的平台发展。但与之不同的是前者在低粘土含量的条件下 (<10 % (wt) )就会表现出似固体行为或非末端行为。这些流变特性还会受到粘土的径厚比、化学特性、聚合物基体的分子结构参数和粘土与基体间的相互作用强度等因素的影响。聚合物基粘土纳米复合材料的流变行为是与其微观结构的形成和演化以及聚合物分子链在特定环境下的粘弹松弛过程紧密联系在一起的。本文综述了插层型、剥离型和聚合物分子链一端受限剥离型聚合物基粘土纳米复合材料在力场作用下的流变特性和粘弹松弛机理方面的研究进展。     

填充聚合物的熔体流变学

颗粒填充聚合物（包括聚合物纳米复合材料）溶体通常表现出模量升高、频率依赖性的改变以及高含量填充体系的屈服行为等与单纯聚合物明显不同的流变行为,并且这些流变特性还会受到填料含量、形状尺寸以及颗粒-聚合物之间相互作用等诸多因素的影响。填充聚合物的宏观流变行为是与其微观结构的形成和演化以及高分子链在特定条件下的阻尼松弛过程密切联系在一起的。本文综述了颗粒填充聚合物（包括聚合物纳米复合材料）在力场作用下的流变性以及各种因素对其流变行为的影响,尤其是着重阐述了聚合物纳米复合材料的流变松弛机理和基于热力学理论建立起来的、描述填充体系熔体流变行为的Leonov模型。     

高性能长链支化聚乙烯制备的研究进展

长链支化聚乙烯（LCB-PE）在聚乙烯链上含有长链的支化结构，因此具有优异的流变性能，从而改善了聚合物的加工性能，这是其它结构聚乙烯所不能比拟的。长链支化聚乙烯的制备方法有辐照法、茂金属共聚法和聚丁二烯加氢法等，本文综述了各种方法的基本原理和优缺点。辐照法制备LCB-PE的优点是比较简便，容易实现工业化生产，但也有制备的LCB-PE结构不明确，高能辐照对设备要求较高的缺点。茂金属共聚法制备的LCB-PE结构较明确，制备过程较易控制，但由于茂金属催化剂的专利问题而不易推广。聚丁二烯加氢法制备的LCB-PE其主链长度、支链长度和支链密度都可控，但过程较复杂，成本高，不易推广。     

高分子材料支化结构与流变性的联系串讲

高分子链结构为直链型或支化型以及高分子支链的形态、多寡和长度对材料的剪切黏度、黏流活化能、熔体破裂现象等流变性能有显著影响,且与高分子材料成型加工行为密不可分。本文以串讲方式讨论了高分子材料支化结构与流变性能之间的联系。理解、串并、归纳和总结高分子支化结构与流变性之间的联系有利于使学生更加深刻领会《聚合物流变学》课程中高分子材料结构与性能间的关系,串联高分子物理、聚合物流变学、高分子材料成型加工系列专业课程知识。     

聚乙酸乙烯酯的溶液性质及长链支化度

用粘度法,GPC和LALLS测定了线型及不同转化率的PVAc分级级份的粘度与分子量。提出了以线型和支化聚合物的K,α计算临界分子量的方法。讨论了表征PVAc长链支化的各种参数与分子量和转化率之间的关系以及不同条件下迭代法计算的支化频率λ的差异。实验结果表明,特性粘数和数均分子量乘积所表示的流体力学体积更适合GPC的普适标定概念。     

高分子材料支化结构与流变性的联系串讲北大核心CSCD

高分子链结构为直链型或支化型以及高分子支链的形态、多寡和长度对材料的剪切黏度、黏流活化能、熔体破裂现象等流变性能有显著影响,且与高分子材料成型加工行为密不可分。本文以串讲方式讨论了高分子材料支化结构与流变性能之间的联系。理解、串并、归纳和总结高分子支化结构与流变性之间的联系有利于使学生更加深刻领会《聚合物流变学》课程中高分子材料结构与性能间的关系,串联高分子物理、聚合物流变学、高分子材料成型加工系列专业课程知识。     

4种低密度聚乙烯树脂的链结构及其性能

选用4种商品化的具有不同熔体流动速率的低密度聚乙烯(LDPE),利用高温凝胶渗透色谱仪(HT-GPC)、碳核磁共振谱仪(¹³C NMR)、差示扫描量热仪(DSC)和流变仪研究其链结构特点及其流变性能。 按照相对分子质量的差异分成两组,D-1和Q-1,D-3和Y-1,每组的两个样品具有相近的平均相对分子质量。 ¹³C NMR的结果表明,4种LDPE都既含有短链支化又含有长链支化,且短链支化含量均高于长链支化含量;而短链支化中丁基含量最多。 连续自成核退火热分级(SSA)结果表明,树脂中均含有不同长度的可结晶的亚甲基序列,即每种树脂分子链内的短链支化分布不均匀。 探讨了相对分子质量及其分布、亚甲基序列长度及其分布、支化含量、结晶度等因素对树脂熔融行为、流变行为和薄膜力学性能的影响,发现Q-1的低相对分子质量尾端和Y-1的长链支化含量均影响熔体流动速率,平均亚甲基序列长度决定熔融峰的位置,结晶度直接影响薄膜的力学性能。 基于上述结果,建立结构与性能的关联。     

链转移剂单体存在下苯乙烯乳液聚合反应研究

以α-甲基丙烯酸-3-巯基己酯(MHM)为链转移剂单体,过硫酸钾(KPS)为引发剂,十二烷基苯磺酸钠(LAS)为乳化剂,通过乳液聚合合成支化聚苯乙烯(BPSt).采用1H-NMR和三检测体积排除色谱(TD-SEC)对聚合反应过程和合成的聚合物进行了表征分析.结果表明,在合适的乳化剂用量、引发剂用量和聚合反应温度等条件下,反应初期生成的初级链可以完全转化成支化聚合物,在高单体转化率下不发生交联得到较窄分子量分布的高分子量支化聚苯乙烯(Mn,SEC1.4×105,Mw,MALLS2.0×106,PDI4.5),而且所得聚合物表现出很高的支化程度(g'=0.5~0.6).     

基于环糊精的高度支化聚合物*

环糊精（CD）与高度支化聚合物都存在空腔结构,若将两者结合起来可构筑出含有两种不同疏水空腔且具有特异物理化学功能的高分子体系,并有望在分子包合与识别、药物控释、基因传输等领域得到新的应用。本文根据高度支化聚合物与环糊精结合方式的不同,从以环糊精为核的高度支化聚合物、外端悬挂环糊精的高度支化聚合物、高度支化聚合物的结构单元与环糊精包合、环糊精与客体分子包合后自组装成高度支化聚合物,以及用功能化的环糊精单体合成超支化聚合物等5个方面对其研究进展进行了总结和评述,并在此基础上展望了该类聚合物的研究方向和发展趋势。     

One‐Pot Synthesis of Novel Branched Polylactide Through the Copolymerization of Lactide with Mevalonolactone

Polylactide, which is a biodegradable and bio‐absorbable polymer having low immunogenicity and good biocompatibility, has been mainly studied for biomedical applications. Branched polymers have different rheological and mechanical properties compared with their linear counterparts owing to their molecular architectures. We synthesized novel biodegradable polylactide having a branched structure composed of metabolically degradable and/or absorbable materials only. The branched polylactide was obtained from a one‐pot copolymerization of L ‐lactide using metabolic intermediate dl ‐mevalonolactone as a bifunctional comonomer having both lactone ring and pendant hydroxy group. The glass transition point, melting point and crystallinity of the branched polylactide are lower than those of linear polylactide.     

Rheological properties of HyperMacs—long‐chain branched analogues of hyperbranched polymers

HyperMacs are long chain branched analogues of hyperbranched polymers, differing only in the sense that they have polymer chains, rather than monomers between branch points. Although the building blocks for HyperMacs and AB₂ macromonomers can be well defined in terms of molecular weight and polydispersity, the nature of the coupling strategy adopted for the synthesis of the HyperMacs results in branched polymers with a distribution of molecular weights and architectures. Melt rheology showed polystyrene HyperMacs to be thermorheologically simple, obeying William–Landel–Ferry behavior. Zero shear viscosities of the polymers were shown to increase with average molecular weight and the melts display shear‐thinning behavior. HyperMacs showed little evidence for relaxation by reptation and the rheological behavior agreed well with the Cayley tree model for hierarchical relaxation in tube models of branched polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2762–2769, 2007     

The linear rheological responses of wedge‐type polymers

The linear rheological responses of a series of specially designed wedge‐type polymers synthesized by the polymerization of large molecular weight monomers have been measured. These wedge polymers contained large side groups which contained three flexible branch chains per polymer chain unit. The master curves for these polymers were obtained by time temperature superposition of dynamic data at different temperatures from the terminal flow regime to well below the glass transition temperature, T_g. While these polymers maintained a behavior similar to that of linear polymers, the influence of the large side group structure lead to low entanglement densities and extremely low rubbery plateau modulus values, being near to 13 kPa. The viscosity molecular weight dependence was also somewhat higher than that normally observed for linear polymers, tending toward a power law near to 4.2 rather than the typical 3.4 found in entangled linear chains. The glassy modulus of these branched polymers is also found to be extremely low, being less than 100 MPa at T_g ?60 °C. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 899–906     

Viscoelastic properties of branched polyethylene melts

The dynamic mechanical properties of branched polyethylenes in the molten state were determined in the frequency range 10^?3–10 radians/sec. The materials tested have remarkably similar rheological properties even though they vary greatly in molecular weight and molecular weight distribution. The similarity in properties is attributed to the influence of long chain branching on the relaxation spectra. A mechanistic argument is proposed to relate the observed behavior to molecular entanglement coupling. The concept of entanglement coupling involving long-chain branching leads to the expectation that the quasi-Newtonian and non-Newtonian viscosities of branched polymers may be either greater or less than those of linear polymers of the same species, which have comparable molecular weights. This is borne out by experiment.     

Rheological and relaxation properties of MQ copolymers

The rheological properties of MQ copolymer melts are investigated under steady-state shear flow and dynamic oscillatory shear within a wide temperature range. The MQ copolymers are highly branched polycyclic compounds (densely crosslinked nanosized networks) incapable of further intermolecular interactions. The samples have identical chemical compositions, but their detailed molecular structures are different. The polymers under consideration show Newtonian behavior in a wide shear-stress range. The values of viscosity vary considerably with the molecular structure of the copolymers. The generalized frequency dependence of complex dynamic modulus components is constructed with the use of the temperature-frequency superposition method. In a first approximation, the viscoelastic behavior of the materials is satisfactorily described by the Maxwell model with a single relaxation time. In this respect, the studied materials are similar to micellar colloids. The relaxation spectra of the copolymers distinguished by narrow distributions are calculated.     

Influence of branching architecture on polymer properties

Hyperbranched polymers (HBPs), invented at the end of 1980s, are one important subclass of the fourth generation macromolecular architectures following the linear, branched, and crosslinking polymers. Due to their unique topological structure and interesting physical/chemical properties, HBPs have attracted wide attention from both academia and industry. HBPs are composed of linear units, dendritic units, and terminal units. The degree of branching (DB), a term to describe the composition of these three structure units and thus the branching architecture of polymers, is one of the most important intrinsic parameters for HBPs. This review has summarized the effect of the DB on the physical and chemical properties of HBPs, including the rheological property, crystallization and melting behaviors, glass transition, thermal and hydrolytic degradations, phase characteristics, lower critical solution temperature phase transition, optoelectronic properties, encapsulation capability, self‐assembly behavior, biomedical applications, and so on. Such a structure and property relationship will build a bridge between the syntheses and applications of HBPs, especially in the application areas of functional materials, biomedical materials, and nanotechnology. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1277–1286, 2011     

Melt rheology of hyperbranched‐polystyrene synthesized with multisite macromonomer

Melt rheological behaviors of hyperbranched‐polystyrene (PS) copolymerized by dendric macromonomer technique are presented. The time–temperature superposition principle was applicable to the hyperbranched‐PS. The branched‐PS showed slightly lower zero‐shear viscosity in comparison with linear PS regardless of a presence of a number of branches expected from the dendric macromonomer technique. Although the influence of use of multimethacryloyl macromonomer in the polymerization process was marginal for linear viscoelastic regime, nonlinear shear and uniaxial elongational flows showed distinct differences between linear and branched‐PS. The strain dependence of the damping function became weak as increase of macromonomer content. The branched‐PS exhibited the growing elongational viscosity function comparing with linear PS. This prominent effect on the elongational flow behavior can be explained by the molecular architecture of the branched‐PS. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2226–2237, 2009     

Viscoelastic properties of decrosslinked irradiation‐crosslinked polyethylenes in supercritical methanol

The viscoelastic properties of decrosslinked irradiation‐crosslinked polyethylenes using a supercritical methanol were investigated via oscillatory dynamic shear measurements. Decrosslinked polymers at a low reaction temperature exhibited solid‐like rheological properties, as evidenced by a small slope at G′ and G″, a long relaxation time, slow stress relaxation behavior, and considerable yield stress. In contrast, decrosslinked polymers at a high temperature exhibited liquid‐like rheological properties that included a large slope in G′ and G″, a short relaxation time, fast stress relaxation behavior, and nonyield stress. The difference in the viscoelastic properties of the decrosslinked polyethylenes was attributed to the difference in the gel content with the reaction temperature. A higher gel content induced stronger solid‐like viscoelastic properties. Hence, the rheological measurements were useful for analyzing the molecular structure of decrosslinked polymers using a supercritical fluid. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1265–1270, 2010